Multi-Length Scale Communication Effects in Catalysis: Thinking Big and Acting Small

The use of hierarchically structured materials as catalysts has been finding increasing application in the past years. For these catalytic systems, not only the nano-scale matters: a high degree of order across multiple length scales, along with its control and analytical assessment, is of paramount importance to obtain innovative properties that can find application in catalysis. Most reviews dealing with hierarchically structured materials are concerned with the "bottom-up" transfer of structural information along the different length scales, with special emphasis on the transmission of chirality. Due to their mesoscale size together with their complex behaviour, these systems are often susceptible to feel the effects of macroscopic forces, that can exert a "top-down" control of their catalytic properties, so that an external stimulus, acting at the level of the supramolecular architecture of the catalyst, can ultimately determine the outcome of the catalyzed reaction at the molecular level. We review in this paper some recent reports that deal with the experimental implementation of this concept, either by using a mechanical force in a full range direct transmission to the reaction coordinate, or by means of a stepwise relay transmission from the macroscopic level (purely supramolecular chirality) to the nanoscopic one. We focus in this review on these multi-length scale communication control effects, identifying the different mechanisms that are affecting the catalytic activity. image